Relaxor Ferroelectric Materials Research Articles

Influence of HFP monomer segments on the crystal structure and electromechanical responses of a P(VDF-TrFE-CFE-HFP) tetrapolymer

The electromechanical properties of PVDF-based polymers, namely converting electrical into mechanical energy, are mainly decided by the crystal structure and domain size of the target product. Thus, we prepare the poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), its terpolymer poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)), and tetrapolymer poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene -hexafluoropropylene) (P(VDF-TrFE-CFE-HFP)) films for comparison, respectively, where the role of the introduction of third and fourth monomers in the electromechanical properties of P(VDF-TrFE) is completely disclosed. Because of introducing CFE and HFP monomers, P(VDF-TrFE) with the ferroelectricity has converted into the relaxor ferroelectric P(VDF-TrFE-CFE-HFP) with a slimmer P-E loop while maintaining good maximum polarization (Pm). Since the nano ferroelectric domains in the relaxor ferroelectric material are easy to reverse along the polarizing electric field, The P(VDF-TrFE-CFE-HFP) sample achieved a dielectric constant (εr) of ∼29 and a strain in the thickness direction (S33) of ∼ -5%, respectively, while the εr and S33 of P(VDF-TrFE) sample are ∼11 and ∼-0.8 %, respectively. This research indicates the availability of the third and fourth monomers for improving the electromechanical effect of such electrostrictive polymers, having wide applications in flexible actuators, transformers, sensors, and so forth.

Energy Storage Performance of (Na0.5Bi0.5)TiO3 Relaxor Ferroelectric Film

The (Na0.5Bi0.5)TiO3 relaxor ferroelectric materials have great potential in high energy storage capacitors due to their small hysteresis, low remanent polarization and high breakdown electric field. In this work, (Na0.5Bi0.5)TiO3 thin films with ~400 nm were prepared on (001) SrTiO3 substrate by pulsed laser deposition technology. The (Na0.5Bi0.5)TiO3 films have good crystallization quality with a dense microstructure and relaxor ferroelectric properties, as confirmed by the elongated hysteresis loops and the relation of <A>∝Eα. A high Eb of up to 1400 kV/cm is obtained, which contributes to a good Wrec of 24.6 J/cm3 and η of 72% in (Na0.5Bi0.5)TiO3 film. In addition, the variations of Wrec and η are less than 4% and 10% in the temperature range of 20–120°C. In the frequency range of 103 Hz–2 × 104 Hz, the variations of Wrec and η are less than 10%. All those reveal the great potential of NBT film for energy storage.

High-entropy relaxor ferroelectric ceramics for ultrahigh energy storage

Dielectric ceramic capacitors with ultrahigh power densities are fundamental to modern electrical devices. Nonetheless, the poor energy density confined to the low breakdown strength is a long-standing bottleneck in developing desirable dielectric materials for practical applications. In this instance, we present a high-entropy tungsten bronze-type relaxor ferroelectric achieved through an equimolar-ratio element design, which realizes a giant recoverable energy density of 11.0 J·cm−3 and a high efficiency of 81.9%. Moreover, the atomic-scale microstructural study confirms that the excellent comprehensive energy storage performance is attributed to the increased atomic-scale compositional heterogeneity from high configuration entropy, which modulates the relaxor features as well as induces lattice distortion, resulting in reduced polarization hysteresis and enhanced breakdown endurance. This study provides evidence that developing high-entropy relaxor ferroelectric material via equimolar-ratio element design is an effective strategy for achieving ultrahigh energy storage characteristics. Our results also uncover the immense potential of tetragonal tungsten bronze-type materials for advanced energy storage applications.

Elastic Relaxor Ferroelectric by Thiol-ene Click Reaction.

As ferroelectrics hold significance and application prospects in wearable devices, the elastification of ferroelectrics becomes more and more important. Nevertheless, achieving elastic ferroelectrics requires stringent synthesis conditions, while the elastification of relaxor ferroelectric materials remains unexplored, presenting an untapped potential for utilization in energy storage and actuation for wearable electronics. The thiol-ene click reaction offers a mild and rapid reaction platform to prepare functional polymers. Therefore, we employed this approach to obtain an elastic relaxor ferroelectric by crosslinking an intramolecular carbon-carbon double bonds (CF=CH) polymer matrix with multiple thiol groups via a thiol-ene click reaction. The resulting elastic relaxor ferroelectric demonstrates pronounced relaxor-type ferroelectric behaviour. This material exhibits low modulus, excellent resilience, and fatigue resistance, maintaining a stable ferroelectric response even under strains up to 70 %. This study introduces a straightforward and efficient approach for the construction of elastic relaxor ferroelectrics, thereby expanding the application possibilities in wearable electronics.

Elastic Relaxor Ferroelectric by Thiol‐ene Click Reaction

AbstractAs ferroelectrics hold significance and application prospects in wearable devices, the elastification of ferroelectrics becomes more and more important. Nevertheless, achieving elastic ferroelectrics requires stringent synthesis conditions, while the elastification of relaxor ferroelectric materials remains unexplored, presenting an untapped potential for utilization in energy storage and actuation for wearable electronics. The thiol‐ene click reaction offers a mild and rapid reaction platform to prepare functional polymers. Therefore, we employed this approach to obtain an elastic relaxor ferroelectric by crosslinking an intramolecular carbon‐carbon double bonds (CF=CH) polymer matrix with multiple thiol groups via a thiol‐ene click reaction. The resulting elastic relaxor ferroelectric demonstrates pronounced relaxor‐type ferroelectric behaviour. This material exhibits low modulus, excellent resilience, and fatigue resistance, maintaining a stable ferroelectric response even under strains up to 70 %. This study introduces a straightforward and efficient approach for the construction of elastic relaxor ferroelectrics, thereby expanding the application possibilities in wearable electronics.

Sm and Mn doped enhancing the electrical properties of .68PMN–.32PT relaxor ferroelectric thin films

Abstract(1−x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 (PMN–PT) has attracted attention due to its excellent electrical properties as a typical relaxor ferroelectric material. High‐quality Mn–Sm co‐doped 0.68PMN–0.32PT thin films were synthesized on the Pt/Ti/SiO2/Si substrates by sol–gel based on spin coating method. The results show that 1 mol% Mn–2 mol% Sm co‐doped PMN–PT thin films have high dielectric constant (εr ∼ 1895) and relatively low dielectric loss (tanδ ∼ .039) at 1 kHz. They also show superior ferroelectric polarization (Pmax ∼ 53.71 μC/cm2, Pr ∼ 30.85 μC/cm2) and high dielectric breakdown strength (∼1656.6 kV/cm), which are primarily due to the low leakage current density (∼10−7 A/cm2). This work suggests a practical approach to enhance the dielectricity, piezoelectricity, and ferroelectricity of PMN–PT thin films.

A Superparaelectric State in Relaxor Ferroelectric (Sr,Bi)TiO3-Bi(Mg,Ti)O3-Modified BaTiO3 Ceramics to Achieve High Energy Storage Performance.

Dielectric ceramic capacitors are highly regarded for their rapid charge-discharge, high power density, and cyclability in various advanced applications. However, their relatively low energy storage density has prompted intensive research aiming at developing materials with a higher energy density. To enhance energy storage properties, research has focused on modifying ferroelectric materials to induce relaxor ferroelectricity. The present study aims to induce a superparaelectric (SPE) state in relaxor ferroelectrics near room temperature by altering BaTiO3 ferroelectric ceramics using the (Sr,Bi)TiO3-Bi(Mg0.5Ti0.5)O3 system ((1-x)BT-x(SBT-BMT)). X-ray diffraction and Raman spectroscopy analysis demonstrated a shift in the crystal structure from tetragonal to cubic with an increasing x content. Notably, the compositions (except x = 0.1) satisfied the criteria for the SPE state manifestation near room temperature. The x = 0.2 specimen displayed characteristics at the boundary between the relaxor ferroelectric and SPE phases, while x ≥ 0.3 specimens exhibited increased SPE state fractions. Despite reduced maximum polarization, x ≥ 0.3 specimens showcased impressive energy storage capabilities, attributed to the enhanced SPE state, especially for x = 0.3, with impressive characteristics: a recoverable energy density (Wrec) of ~1.12 J/cm3 and efficiency (η) of ~94% at 170 kV/cm applied field. The good stability after the charge-discharge cycles reinforces the significance of the SPE phase in augmenting energy storage in relaxor ferroelectric materials, suggesting potential applications in high-energy density storage devices.

Exploring Local Order/Disorder in Relaxor Ferroelectric Materials via TEM and STEM Methods

Exploring Local Order/Disorder in Relaxor Ferroelectric Materials via TEM and STEM Methods

Highly elastic relaxor ferroelectric via peroxide crosslinking.

Relaxor ferroelectrics are well-known for their high dielectric constants, low dielectric losses, and excellent electromechanical properties, making them valuable for various electronic devices. Despite recent efforts to enhance the durability of ferroelectrics through chemical cross-linking, achieving elasticity in relaxor ferroelectric materials remains a significant challenge. These materials inherently possess traits such as low crystallinity and small crystal size, while chemical crosslinking tends to diminish polymer crystallinity considerably. Thus, a key obstacle to making relaxor ferroelectric polymers elastic lies in safeguarding their crystalline regions from the effects of slight crosslinking. To tackle this issue, we selected P(VDF-CTFE-DB) with highly reactive C[double bond, length as m-dash]C double bonds as crosslinking sites, reducing the amount of cross-linking agents added and thereby lessening their impact on crystallinity. Through peroxide crosslinking, we transformed linear P(VDF-CTFE-DB) into a network structure, successfully producing a resilient relaxor ferroelectric material with maintained polarization intensity for ferroelectricity. Notably, this elastic relaxor ferroelectric was synthesized at relatively low temperatures, exhibiting a remarkable dielectric constant, superior resilience, fatigue resistance, and a stable ferroelectric response even under strains of up to 80%. Our approach paves the way for developing low-cost, high-dielectric-constant elastomers suitable for wearable electronics and related applications.

Highly elastic relaxor ferroelectrics for wearable energy storage.

Polymer-based relaxor ferroelectrics with high dielectric constant are pivotal in cutting-edge electronic devices, power systems, and miniaturized pulsed electronics. The surge in flexible electronics technology has intensified the demand for elastic ferroelectric materials that exhibit excellent electrical properties and mechanical resilience, particularly for wearable devices and flexible displays. However, as an indispensable component, intrinsic elastomers featuring high dielectric constant and outstanding resilience specifically tailored for elastic energy storage remain undeveloped. Elastification of relaxor ferroelectric materials presents a promising strategy to obtain high-dielectric elastomers. In this study, we present a strain-insensitive, high elastic relaxor ferroelectric material prepared via peroxide crosslinking of a poly(vinylidene fluoride) (PVDF)-based copolymer at low temperature, which exhibits an intrinsic high dielectric constant (∼20 at 100 Hz) alongside remarkable thermal, chemical, and mechanical stability. This relaxor ferroelectric elastomer maintains a stable energy density (>8 J cm-3) and energy storage efficiency (>75%) under strains ranging from 0 to 80%. This strain-insensitive, high elastic relaxor ferroelectric elastomer holds significant potential for flexible electronic applications, offering superior performance in soft robotics, smart clothing, smart textiles, and electronic skin.

A novel lead‐free relaxor with endotaxial nanostructures for capacitive energy storage

AbstractDielectric capacitors with a fast charging/discharging rate, high power density, and long‐term stability are essential components in modern electrical devices. However, miniaturizing and integrating capacitors face a persistent challenge in improving their energy density (Wrec) to satisfy the specifications of advanced electronic systems and applications. In this work, leveraging phase‐field simulations, we judiciously designed a novel lead‐free relaxor ferroelectric material for enhanced energy storage performance, featuring flexible distributed weakly polar endotaxial nanostructures (ENs) embedded within a strongly polar fluctuation matrix. The matrix contributes to substantially enhanced polarization under an external electric field, and the randomly dispersed ENs effectively optimize breakdown phase proportion and provide a strong restoring force, which are advantageous in bolstering breakdown strength and minimizing hysteresis. Remarkably, this relaxor ferroelectric system incorporating ENs achieves an exceptionally high Wrec value of 10.3 J/cm3, accompanied by a large energy storage efficiency (η) of 85.4%. This work introduces a promising avenue for designing new relaxor materials capable of capacitive energy storage with exceptional performance characteristics.

Atomic‐scale insights into electronic, structural, dielectric, and ferroelectric properties of Ba(Zr, Ti)O3 perovskites

Ba(Zr, Ti)O3 perovskites are promising lead-free piezoelectric and relaxor ferroelectric materials for energy storage and harvest devices, of which the ferroelectric mechanism has long been ambiguous. We theoretically investigated the ferroelectric mechanism from the electronic and atomic scale using first-principles calculation based on density functional theory and density functional perturbation theory. With increasing zirconium content, it is obtained a lattice expansion and a decrease in the ferroelectric polarization in agreement with experiment. An unstable zone-center phonon mode is observed in the polar ferroelectric phase, which tends to stabilizein the nonpolar paraelectric phase, which is associated with the engineering of the relative displacement of the B-site ions that alters the short-range force. The newly formed Ti/Zr (dzx,dyz)-O (2px,2py) π-type bonds are discovered to be the origin of the Ba(Zr, Ti)O3ferroelectric instability and polarization. Local relaxation strains caused by lattice misalignment of the ionic displacements of Ti ions and Zr ions suppress the polarization of Ba(Zr, Ti)O3 by counteracting the off-centering of Ti ions and adjacent Zr ions in certain directions.

Multi-functional piezoelectric nanogenerator based on relaxor ferroelectric materials (BSTO) and conductive fillers (MWCNTs) for self-powered memristor and optoelectronic devices

Nowadays self-charging memristors and photodetectors open the path for future research into energy-autonomous electronics which hold the promise of enabling exceptionally efficient applications in memory storage, small portable electronics, neuromorphic computing, and optoelectronics devices. Hence, in the recent era, much research work has been focused on the development of nanogenerators for technological applications. In this regard, the main aim of the present study is to develop a multi-functional piezoelectric nanogenerator based on relaxor ferroelectric materials having three-phase MWCNTs/BSTO/PVDF nanocomposites. BSTO and CNT fillers promote >80 % electroactive phase nucleation in PVDF, making it appropriate for piezoelectric energy harvesting devices. Incorporating conductive fillers (CNTs) and dielectric fillers (BSTO) into the PVDF matrix enhances the piezoelectric nanogenerator's dielectric, ferroelectric, and output performance. PENG based on an optimized BSTO-CNTs-PVDF composite (with 20 % BSTO and 0.20 % CNTs loading) produced an output power of 31.5 µW with a high open-circuit voltage of 42 V and a short-circuit current of 9 µA, it demonstrates enough capability to power up small portable electronic devices. This work can also be used for a realistic technique for generating self-powered memristors and photodetectors for extremely efficient memristive neural networks and optoelectronics devices. Demonstration of power generation of the prepared device by different activities is demonstrated.

The unexpected diffuse phase transition in relaxor-PbTiO3 ferroelectrics via acceptor modification

The diffuse phase transition (DPT) and domain structure are essential to the functional properties of relaxor ferroelectrics and are extremely sensitive to the ion doping. The utilization of acceptor doping has been observed to be an effective method in enhancing the high-power properties of relaxor ferroelectric materials. The present study aims to examine the acceptor-doped DPT and domain structure in single crystals of Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3. An unexpected physical phenomenon was identified in which Mn-doping increased dielectric diffusion and lowered domain size while suppressing dielectric relaxation. Traceability investigations suggest that Mn-doping inhibited the growth of polar nanoregions by enhancing random electric fields, which increases dielectric diffusion while decreasing the domain size. Meanwhile, Mn doping redistributes the relaxation time function, which results in a reduction in dielectric relaxation. The current research deepens the understanding of the physical basis of DPT and can be applied to the development of high-performance piezoelectric materials.

Extension of Surface Charge Density Studies of Metal Oxide Semiconductor (MOS) Structure to Polarization Studies of Metal Ferroelectric Metal (MFM) Structure in Bulk Form: Experimental and Simulation of Polarization Data

Ba(NdxTi(1-2x)Nbx)O3 and (Na0.5Bi0.5)(NdyTi1-2yNby)O3 relaxor ferroelectric materials were prepared through solid state sintering route. The polarization as a function of electric field (PE loops) were measured with Radiant technologies PE loop tracer. In the present studies we have extended the surface charge density studies of metal oxide semiconductor (MOS) structure to the polarization studies of metal ferroelectric and metal (MFM) structure in bulk form by combining it with the modified Glazounov and Arrhenius equations. The simulation is in good agreement the experimental data. In the case of Ba(NdxTi(1-2x)Nbx)O3 ceramics the value of dipole moment (p) are 2.24x10−26 C.m, 1.80x10−26 C.m, 2.23x10−26 C.m & 2.21x 10−26 C.m for x = 0.025, 0.05, 0.1 & 0.2, respectively. The values of surface potential (Ψp) are 466 meV, 503 meV, 552 meV & 505 meV for x = 0.025, 0.05, 0.1 & 0.2, respectively.

Outstanding Energy Storage Performance of NBT-Based Ceramics under Moderate Electric Field Achieved via Antiferroelectric Engineering.

Ultrahigh energy-storage performance of dielectric ceramic capacitors is generally achieved under high electric fields (HEFs). However, the HEFs strongly limit the miniaturization, integration, and lifetime of the dielectric energy-storage capacitors. Thus, it is necessary to develop new energy-storage materials with excellent energy-storage densities under moderate electric fields (MEFs). Herein, the antiferroelectric material Ag0.9Ca0.05NbO3 (ACN) was used to modify the relaxor ferroelectric material 0.6Na0.5Bi0.5TiO3-0.4Sr0.7Bi0.2TiO3 (NBT-SBT). The introduction of ACN results in high polarization strength, regulated composition of rhombohedral (R3c) and tetragonal (P4bm), nanodomains, and refined grain size. An outstanding recoverable energy density (Wrec = 4.6 J/cm3) and high efficiency (η = 82%) were realized under an MEF of 260 kV/cm in 4 mol % ACN-modified NBT-SBT ceramic. The first-principles calculation reveals that the interaction between Bi and O is the intrinsic mechanism of the increased polarization. A new parameter ΔP/Eb was proposed to be used as the figure of merit to measure the energy-storage performance under MEFs (∼200-300 kV/cm). This work paves a new way to explore energy-storage materials with excellent-performance MEFs.

Enhancement of energy storage performance in lead‐free relaxor ferroelectric ceramics via band structure engineering

AbstractDielectric capacitors with excellent energy storage performance (ESP) are in great demand in the power electronics industry due to their high power density. For the dielectric materials, the dielectric breakdown strength (BDS) is the key factor to improve ESP, which is the focus and bottleneck of current research, especially in the relaxor ferroelectric (RFE) materials with already low residual polarization (Pr). Here, we stimulate the ESP of the BaTiO3 (BT)‐based RFE ceramics by band structure engineering. The Ta element is selected to enhance the band gap of doped ceramics, occupying Ti‐site in supercell of BT and optimizing the bonds length of Ti‐O bond to increase the energy band of Ti 3d states. In this way, the band gap of the doped ceramics is efficiently enhanced from 1.8 eV to 2.22 eV resulting in the large BDS. Prospectively, combined with the advantage of fine grain size, the highest recoverable energy storage density (Wrec) of 2.85 J/cm3 is obtained at 350 kV/cm and the ultra‐high energy efficiency (η) of 95.26% is found at 200 kV/cm. Our work reveals the relationship between elements doping in B‐site and band structure, being expected to benefit for designing energy storage materials.

Structural, dielectric, and morphological properties of (1-x)Ba0.65Sr0.35TiO3-xBi(Mg2/3Nb1/3)O3

Compared to other electrical energy storage devices, dielectric capacitors provide advantages like high power density, fast charge and discharge times, thermal stability, excellent mechanical strength, and a long cycling lifetime. Amongst the various dielectric materials, relaxor ferroelectric materials offer low remanent polarization and high energy efficiency. Previous research has shown that (i) doping Bi3+ ions into perovskite material can achieve improved results because its valence electronic configuration is close to that of Pb2+ and its ionic radius is also comparable to that of Ba2+, and (ii) introducing complex ions at the B-site can reduce the long-range ferroelectric order and result in the occurrence of polar nano regions.The present work aims at (i) incorporating both these strategies for the synthesis of the dielectric ceramic material and (ii) studying the structural, morphological, and dielectric properties of the prepared material. We have successfully synthesized (1-x) Ba0.65Sr0.35TiO3 – x BiMg2/3Nb1/3O3 with the help of a conventional solid-state reaction technique. The XRD analysis demonstrates the formation of cubic perovskite structure with space group Pm3m. The diffraction peaks shift towards lower 2θ angles with an increasing concentration of BMN, indicating a regular increase in unit cell volumes owing to the substitution of the smaller Ti4+ ions with bigger Mg2+ and Nb5+ ions. FESEM images illustrate the development of a homogeneous and dense microstructure. Element mapping analysis confirms the uniform distribution of all the elements within the prepared sample. From the dielectric measurements, we found that with the increase in doping, the dielectric peak broadens, and the frequency dispersion increases, indicating a rise in the relaxor behavior, which may be attributed to the increase in cation disorder due to the substitution of Bi3+ and [Mg2/3Nb1/3]4+ at the A- and B-site, respectively. The excellent dielectric properties indicate that (1-x)BST-xBMN is a promising ceramic material for use as a dielectric in capacitors for advanced pulsed power applications and consumer electronic devices.

Finite element analysis of transverse size effect on the pyroelectric Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3 –PbTiO3 thin film for infrared array applications

Exploring and revealing the influence of the pyroelectric thin film array element size on its structure and pyroelectric performance is crucial for designing integrated pyroelectric infrared detectors. In this work, the transverse size effect on the piezoelectric, dielectric, and especially the pyroelectric properties for a new-generation relaxor ferroelectric material Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 (PIMNT) was studied by a finite element method. The lateral size-dependent piezoelectric and dielectric properties of the PIMNT thin film indicated that with the decrease in the transverse size, the piezoelectric constant d33 and relative dielectric constant εr increased substantially. The piezoelectric constant d33 and relative dielectric constant εr along ⟨001⟩ and ⟨011⟩ orientation increased faster than those along ⟨111⟩. A critical aspect ratio (in this paper, it was defined as radius/thickness) was found around 1:1 for three directions. We further discovered that the pyroelectric coefficient for PIMNT thin film along the ⟨111⟩ direction (the best crystallographic orientation for pyroelectric performance) decreased from 8.5 × 10−4 to 8.0 × 10−4 C/(m2·K) with the aspect ratio down to 0.01. The variation of the piezoelectric, dielectric, and pyroelectric properties originated from the declamping of the PIMNT thin film from the substrate. This finding gives insight into the transverse size effect on the electrical properties of new-generation relaxor PIMNT thin film and provides a guidance for designing high-performance infrared array detectors.

Anisotropy free energy contribution of the ferroelectric domain dynamics in PMN‐PT and PIN‐PMN‐PT relaxor ferroelectrics

AbstractA direct correlation between the materials property behavior with its associated ferroelectric domain mechanisms and the anisotropic component of the Landau free energy is established for binary PMN‐PT (generation I) and ternary PIN‐PMN‐PT (generation II) relaxor ferroelectric single crystal material systems. In addition to their trade‐off in material properties, the observed ferroelectric domain dynamic and the determined free energy anisotropies, especially as approaching phase transition, provide direct insights into the materials field‐dependent behavior between the binary and ternary ferroelectric systems. Domain configuration features such as lamellar structures in binary PMN‐PT and concentric oval‐like structures in ternary PIN‐PMN‐PT result in different material responses to external stimuli. Compared to binary PMN‐PT, the concentric oval‐like domain structures of ternary PIN‐PMN‐PT result in a 20°C higher temperature range of field‐dependent linear behavior, 40% increase in coercive electric field higher elastic stiffness during ferroelectric domain switching, and lower electromechanical energy losses. Separation of the isotropic and anisotropic components in the Landau free energy reveals a higher anisotropic free energy contribution from the ternary system, especially at temperature for practical applications. The high anisotropic free energy found in the ternary PIN‐PMN‐PT system implies that the concentric oval‐like domain structure contributes to reduced electromechanical energy losses and enhanced stability under external applied fields.